Systems and methods for refining coal into high value products

ABSTRACT

Described herein are integrated thermochemical processes for the conversion of coal into high-value products using a combination of pyrolysis and solvent extraction. The described systems and methods are versatile and may be used to generate a variety of high value products including chemicals (aromatics, asphaltenes, napthenes, phenols, polyamides, polyurethanes, polyesters), polymer composite products (resins, coatings), graphitic products, agricultural materials, building materials, carbon fiber and other products that are substantially more valuable that the energy generated via combustion. Further, these systems and methods are specifically designed to be highly branched and highly flexible, allowing for a high selectivity and optimization for increasing the value of the products relative to the feedstock.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims the benefit of and priority to U.S.Provisional Patent Application No. 62/557,804 filed Sep. 13, 2017 whichis hereby incorporated by reference to the extent not inconsistentherewith.

BACKGROUND OF THE INVENTION

Coal mining and production represents a large, valuable industry in boththe United States and abroad. The vast majority of this coal iscombusted to generate energy. Currently, there is a great deal ofeconomic and political pressure on the building of new coal-fired powerplants. Accordingly, to further utilize coal beyond combustion, itbecomes increasingly attractive to investigate use as a feedstock forother processes, including for the production of chemicals, plastics,building materials and products which may have significantly highervalue than that of the energy produced by power plants.

Research and development into coal as a feedstock for the generation ofchemicals and other materials has been around for more than 50 years.Interest in this field has typically increased during periods in whichtraditional petroleum feedstocks have become expensive due to high oilprices, such as in the 1970's. For example, U.S. Pat. No. 4,346,077discusses pyrolysis of coal to generate liquid hydrocarbons and vapors.U.S. Pat. No. 9,074,139 describes generation of aromatic compounds fromcoal utilizing liquefaction and hydrocracking. Common amongst thesereferences and most coal conversion technology is that coal is beingconverted into coal tars to mimic petroleum hydrocarbons in such a waythat it can then be processed through a petroleum refinery. Coal, whichgenerates a greater amount of solid products and typically contains ahigh sulfur content and some metals, often makes a relatively poorsubstitute for processes designed for oil-based feedstocks.

It can be seen from the foregoing that there remains a need in the artfor systems and methods for the deliberate, thermochemical conversion ofcoal into intermediate and finished high-value products, therebygenerating materials that are far more valuable than the equivalentcoal-based energy produced via combustion. Further, separation andprocess systems and methods are needed that are specifically tailoredand/or customized to coal and coal-based feedstocks to achieve effectivetransformation into products, that consider yields, efficiency,conversion rates and the manufacture of distinguished goods that can besold.

BRIEF SUMMARY OF THE INVENTION

Described herein are integrated thermochemical processes for thedeliberate decomposition, extraction and conversion of coal intohigh-value products and goods using a combination of pyrolysis andsolvent extraction. The described systems and methods are versatiledeliberate and may be used to generate a variety of intermediate andfinished high value products including chemicals (aromatics,asphaltenes, napthalenes, phenols and precursors for the production ofpolyamides, polyurethanes, polyesters, graphitic materials), polymercomposite products (resins, coatings, adhesives), agriculturalmaterials, building materials, carbon fiber, graphene products and othermaterials that are substantially more valuable that the energy generatedvia combustion. Further, these systems and methods are specificallydesigned to be highly branched (i.e. process steps that together areamenable to produce wide ranging product types and specifications fromthe same feedstock), as well as being synergistic (e.g. permittingcombining resin systems produced from coal with solid carbon materialderived from coal to make composite materials). Thus the systems andmethods are highly adaptive to markets and responsive to product demand.Thus, allowing for a high selectivity and optimization for increasingthe value of the actual products relative to the feedstock. Some ofthese products may be coal extracts such as metals and rare earthelements.

The provided thermochemical processes convert a large portion of thecoal feedstock into and extracts from coal value added products and mayfocus on converting a high percentage (e.g. greater than 50% dry basis)of the solid material into fluids. These systems and methods may avoidexpensive, energy intensive hydrocracking and hydrotreating processes.The thermochemical processes described herein use an integratedcombination of thermal and chemical processes to provide controlled anddeliberate conversion of coal and extraction from coal into a selectiveand switchable mix of high-value products that may be optimized toachieve profitable manufacturing motivated by the total value of goodsgenerated.

In an aspect, provided is a method for converting coal into a pluralityof high value coal products comprising: i) providing a feedstock,wherein the feedstock is at least partially derived from coal; ii)processing the feedstock, wherein the processing step includes acombination of pyrolysis and solvent extraction, wherein the pyrolysisand solvent extraction are integrated and carried out under conditionsfor generating a plurality of high value coal products. The percentageof high value coal products that are liquid at standard temperature andpressure may be greater than or equal to 50% dry basis, greater than orequal to 60%, or optionally, greater than or equal to 70%. The step ofprocessing may be highly branched, discriminating and wide ranging, yethighly selective.

Pyrolysis is generally used in the described systems to reduce the sizeor length of the complex molecules commonly found in coal and toconcentrate extracts. Pyrolysis as described herein may refer to flashpyrolysis, for example, having small residence times (on the order ofseconds) at high temperatures. The pyrolysis processes described hereinmay, in some embodiments, specifically exclude the use of a catalystand, in some embodiments, specifically include the use of a catalyst.The pyrolysis processes described herein may, in some embodiments behighly selective.

Pyrolysis may be a single stage pyrolysis, multiple single stagepyrolysis, a single multistage pyrolysis, multiple multistage pyrolysisor a combination of single stage and multistage pyrolysis steps. Eachpyrolysis or pyrolysis step may independently be performed at a pressureselected from the range of 0.5 atm to 15 atm, 0.9 atm to 15 atm, or 0.9atm to 10 atm. Each pyrolysis or pyrolysis step may be performed at atemperature selected from the range of 400° C. to 1200° C., 750° C. to1200° C., or optionally, 900° C. to 1100° C. In an embodiment, theresidence time for pyrolysis is selected over the range of 30 minutes to0.1 seconds and optionally less than or equal to 10 seconds, 5 seconds,2 seconds, or 1 second. Pyrolysis may be integrated with solventextraction, as a pretreatment or post treatment. In each pyrolysis orpyrolysis step may independently be performed at a pressure selectedfrom the range of 0.5 atm to 15 atm, 0.9 atm to 15 atm, or 0.9 atm to 10atm.

Solvent extraction may generate a mass percentage of gas, excludingwater vapor, less than or equal to 25%, less than or equal to 15%, lessthan or equal to 10%, less than or equal to 5%, or optionally, less thanor equal to 3%. Solvent extraction may generate a mass percentage ofliquid, which may include or exclude the solvent itself up to 100%,which itself becomes a precursor or intermediate for further processinginto goods and products. Pyrolysis may be performed in nitrogen, air orhydrogen-donating environment such as in the presence of hydrogen gas,methane, syngas or any combination thereof. Pyrolysis may be flashpyrolysis.

Solvent extraction is generally used to remove and/or separate variouscomponents of the solid feedstock including the intermediates and endproducts. It should be noted, that in some instances solvent extractiondoes facilitate chemical reactions including conversion of solidmaterial into liquids and may chemically alter the various componentsbeing processed. Various solvents known in the art may be used,including aliphatic, aromatic, hydrogen donating, non-polar solvents,polar solvents and ionic liquid solvents. Solvent extraction may includemultistage extraction and multiple solvent extraction steps ahead orfollowing pyrolysis. Solvent extraction may include super critical fluidsteps. Solvent extraction may also utilize fractionation, or the use ofmultiple solvent extraction steps at different temperatures andpressures. Various uses of solvent recovery, including solvent recyclingmay provide additional efficiency and cost savings in addition to thesolvent being a precursor or intermediate product for further processingin itself.

Solvent extraction, as described herein, may be performed with at leastone liquid solvent. The at least one solvent may be selected from thegroup consisting of an aliphatic solvent, an aromatic solvent, a polarsolvent, a hydrogen donating solvent, an ionic liquid solvent and anycombination thereof. Solvent extraction may use at least two liquidsolvents. The first solvent may be a polar solvent, a combination ofsolvents which may include polar and aromatic solvents appliedseparately. The second solvent may be a hydrogen donating solvent orvice versa. The solvent extract itself may be an intermediate that isfurther processed into a finished product.

Solvent extraction may be a single stage solvent extraction, multiplesingle stage solvent extractions, a single multistage solventextraction, multiple multistage solvent extractions or a combination ofsingle stage and multistage solvent extractions. Solvent extraction maybe performed at a temperature less than the critical temperature of thesolvent. Each Solvent extraction or step may independently be performedat less than or equal to 400° C., less than or equal to 350° C., oroptionally, less than or equal to 300° C. Solvent extraction maygenerate a mass percentage of gas, excluding water vapor, less than orequal to 10%, less than or equal to 5%, or optionally, less than orequal to 1%.

Solvents as described herein may comprise tetralin(1,2,3,4-Tetrahydronaphthalene), 1-methyl-napthalene, toluene,dimethylformamide (DMF) or any combination thereof. A solvent may beimpure, for example, due to recycle or separation inefficiencies.

The described systems and method are flexible and the solvent extractionstep may be performed prior to the pyrolysis step and vice versa.Further, systems that are more complex may utilize multiple pyrolysissteps and/or multiple solvent extraction steps in any combination, forexample, a first pyrolysis step followed by a first solvent extractionand then a second pyrolysis step. Additionally, recycle streams may beutilized such that a portion the output from one step (either pyrolysisor solvent extract) may be recycled and used as in input or as a portionof an input for a previous step, subsequent step or current step. Thesolvent extraction and pyrolysis steps may be considered as integratedachieving results that pyrolysis and/or solvent extraction cannotachieve alone.

The solvent extraction may be performed upstream of the pyrolysis. Thepyrolysis may be performed upstream of the solvent extraction. A portionof products from the pyrolysis step may be recycled to the solventextraction. A portion of products from the solvent extraction may berecycled to the pyrolysis or sent for further downstream processing. Theprocessing step may comprise multiple solvent extractions and solventsfrom a later solvent extraction may be recycled to an earlier solventextraction or the pyrolysis step.

The primary feedstocks described herein are generally coal orcoal-based, including run of mine coal and/or coal, which may bephysically, chemically and/or thermally pre-processed which may includedrying and vapors recovery. Pre-processing may include pulverizing,de-ashing and/or drying. The described systems and methods are flexibleand may be used with any primary feedstock including lignite,subbituminous and bituminous coal. Secondary feedstocks inclusions mayinclude other hydrocarbon sources such as biomass and oil shale and/orinclusion of secondary recycle streams from downstream processes e.g.syngas and other reactive mineral resources such as trona.

High value coal products described herein have a monetary or economicvalue significantly higher than the value of the energy produced byburning or combusting the primary feedstock. High value coal productsmay comprise a minority manufacture of fuels products and/or blendingcomponents, such as less than or equal to 10% fuel products and/orblending products, less than or equal to 5% fuel products and/orblending products, or optionally, less than or equal to 3% fuel productsand/or blending products. High value coal products may comprise polymersor polymer precursors. High value coal products may comprisepolyurethane. High value coal products may comprise compositepolyurethane foam. High value coal products may comprise polyamides.High value coal products may comprise polyesters. High value coalproducts may comprise aromatics. High value coal products comprisebenzene, toluene, xylenes (including isomers), phenols, cresols,xylenols (including isomers), naphthenols, C9 single ring aromatics(including isomers), C10 single ring aromatics (including isomers) orany combination thereof. High value coal products may compriseparaffins, olefins, asphaltenes, napthenes or a combination thereof.High value coal extractive products may include metals and rare earthelements.

High value coal products may comprise asphaltenic intermediates and/orfinished products. High value coal products may comprise road paving androofing intermediates, additives or finished products. High value coalproducts may comprise coal tar, distillates, pitch, asphalt, graphiticmaterials, carbon fibers or any combination thereof. High value coalproducts may comprise soil amendments and fertility products. High valuecoal products may comprise building materials. A significant portion ofthe high value coal products may be solids, for example, greater than orequal to 10% solids, greater than or equal to 20% solids, or optionally,greater than or equal to 30% solids. The solids may be converted tographitic materials, construction materials, composite materials, liquidadditives or any combination thereof when combined a resin, liquid orother bi-product generated by the methods described herein. High valueproducts may include syngas, urea, CO₂ and/or acetylene.

In an aspect, provided is a method for converting coal into a pluralityof high value coal products comprising: i) providing a primary feedstockat least partially derived from coal; ii) processing the primaryfeedstock, wherein the processing sequence is a) a pyrolysis step,wherein the pyrolysis step is performed in less than or equal to 10seconds performed in a hydrogen rich atmosphere; and b) a solventextraction step, wherein the solvent extraction step is performed withat least one liquid solvent, wherein the liquid solvent is selected fromthe group consisting of: a polar solvent, and/or a hydrogen donatingsolvent and/or any combination thereof; c) wherein the pyrolysis step isthe first process step carried out on the primary feedstock and whereinthe solvent extraction process is the second process step carried out onthe solid char produced from the pyrolysis; d) wherein the pyrolysis andsolvent extraction process are integrated and carried out underconditions for generating a plurality of high value coal products.

The pyrolysis step may be a flash pyrolysis process. The solventextraction step may be a single stage solvent extraction, multiplesingle stage solvent extractions, a single multistage solventextraction, multiple multistage solvent extractions or a combination ofsingle stage and multistage solvent extractions. The solvent extractionstep may use two or more solvents. Processing the feedstock may furthercomprise one or more separation steps occurring after the pyrolysis,after the solvent extraction process or in between multiple solventextractions.

Without wishing to be bound by any particular theory, there may bediscussion herein of beliefs or understandings of underlying principlesrelating to the devices and methods disclosed herein. It is recognizedthat regardless of the ultimate correctness of any mechanisticexplanation or hypothesis, an embodiment of the invention cannonetheless be operative and useful.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

FIG. 1 provides an overview of the described process includingadditional post-processing to generate liquid and solid products.

FIG. 2 provides an example processing step where pyrolysis is followedby solvent extraction.

FIG. 3 provides an example of a multistage solvent extraction step wheretwo different solvents are used to increase extraction effectiveness.

FIG. 4 provides an overview including inputs and outputs.

FIG. 5 is an example of a highly branched, highly selective processutilizing solvent extraction and pyrolysis.

FIG. 6 is an example of a highly branched, highly selective processutilizing solvent extraction and pyrolysis.

FIG. 7 provides an example overview with high detail regarding productsand additional processes.

FIG. 8 provides additional examples of integrated, multistage processingsteps.

FIG. 9 provides example thermochemical processing steps.

DETAILED DESCRIPTION OF THE INVENTION

In general, the terms and phrases used herein have their art-recognizedmeaning, which can be found by reference to standard texts, journalreferences and contexts known to those skilled in the art. The followingdefinitions are provided to clarify their specific use in the context ofthe invention.

As used herein, “feedstock at least partially derived from coal” refersto a solid, powder, slurry, liquid, fluid or other material that hasbeen generated from a raw coal source. For example, raw coal may becrushed into a powder prior to processing. The feedstock may havevarious physical, thermal and chemical pretreatments known in the art tofurther facilitate processing of the feedstock, for example, by flashpyrolysis and solvent extraction. The feedstock may also act as arecycled stream from one or more of the downstream processes orintermediates (e.g. solid material remaining after solvent extraction)so that additional products, such as liquid products, may be promoted byreprocessing less valuable or unwanted intermediate products.

“Coal” refers to predominately solid hydrocarbons that may contain someamount of fluid material. Coal is generally composed of hydrogen,carbon, sulfur, oxygen and nitrogen. Coal, as described herein, mayrefer to bituminous coal, subbituminous coal and lignite. Coal may alsorefer to ash or peat.

“Flash Pyrolysis” as described herein, refers to a thermal process inwhich a feedstock or intermediate product is exposed to sufficientenergy to rapidly heat the feedstock or intermediate. Flash pyrolysismay, for example, provide heat or heat the material being processed totemperatures of greater than 750° C., greater than 900° C., greater than1050° C., or optionally, greater than 1200° C. Flash pyrolysis may referto a heating or resonance time of less than 60 seconds, less than 10seconds, less than 5 seconds, less than 1 second, or optionally, lessthan 0.5 seconds. Flash pyrolysis may be performed in a vacuum, in thepresence of air, or optionally, in the presence of a purified gas suchas hydrogen or methane or syngas. It may also be performed in an inertatmosphere notably at very high temperatures greater than 1200° C.

“Solvent extraction” refers to the process of flowing a liquid solventthrough or across a feedstock or intermediate product to facilitate theextraction components of the material via chemical reaction and/or masstransfer via solubility in the solvent. As described herein, solventextraction may utilize one or more solids in one or more solventextraction steps, including in multistage solvent extractions in whichthe same or similar solvents are repeatedly used on a materials.Solvents, as described herein, may be mixtures including mixtures ofliquid hydrocarbons generated by the processes described herein.Solvents, as described herein, may be mixtures of a number of solvents.Solvents may be recycled and reused as is known in the art. Solventextraction may be at subcritical temperatures. Solvent extraction may beperformed at reduced pressures, atmospherics pressures or increasedpressures.

“Solvent” as described herein refers to a liquid or a mixture of liquidsor cocktails having solubility with regard to hydrocarbons or otherspecies and molecules present in coal. Solvent may refer to a complexmixture of liquids, including hydrocarbon mixtures generally defined byboiling point ranges. Solvents may be polar, paraffinic, aromatic,alcohol, ionic, and/or hydrogen-donating in nature. In embodimentsutilizing two or more solvents, solvents may be distinguished bycomposition, additives, molecular design, boiling point ranges or acombinations thereof.

“High Value Coal Products” describe chemicals and materials (both solidand liquid) generated by the processes described herein that are morevaluable than the coal or feedstock at least partially derived fromcoal. High value coal products may refer to liquid products generatedfrom predominately solid coal. The high value coal products describedherein may have a 1.5×, 2×, 3×, 5×, 10×, or optionally, at least 50×monetary value in comparison with the coal or raw coal material providedin the feedstock. High value coal products may refer coal products thatare 1.5×, 2×, 3×, 5×, 10×, or optionally, at least 50× more valuablethan the energy that would be produced via burning of the coal. Highvalue coal products may refer to products that are not fuel (e.g.created for the purpose of burning to generate energy). Examples of highvalue coal products include polymers (e.g., polyurethane, polyesters,polyamides), high value chemicals (BTX, paraffins, olefins,asphaltenes), composite materials, carbon fiber, graphene, buildingmaterials, road, paving and roofing materials and soil amendments. Highvalue coal products may represent a fraction of the total materialconverted from the feedstock, for example, 50% of the total products ona dry basis, 70% of the total products on a dry basis, 80% of the totalproducts on a dry basis, or optionally, 90% of the total products on adry basis.

“Hydrogen rich environment” refers to an atmosphere comprising a largecomposition of hydrogen gas. Hydrogen rich environment may refer to anatmosphere comprising greater than or equal to 50 mole percent hydrogen,or in some embodiments, greater than or equal to 70 mole percenthydrogen. Hydrogen rich environment may refer to the atmosphere orconditions of a chamber or vessel in which pyrolysis is performed.

“Inert atmosphere” refers to an environment in which the gas phase ischemically inactive with the feedstock(s) present.

Pressure values described herein are provided as absolute pressurevalues, unless otherwise indicated.

The following examples further illustrate the invention but, of course,should not be construed as in any way limiting its scope.

Example 1—Coal Refining Process Overview

This example demonstrates a high-level overview of methods for thethermochemical decomposition of coal or a coal-based feedstock intodeliberately selected high value products. FIG. 1 provides an overviewschematic. In FIG. 1, a feedstock at least partially derived from coalis feed into a processing step 100 that comprises pyrolysis and solventextraction. Generally, the steps of pyrolysis and solvent extraction mayoccur in any order and may include multistage processes, additionalsteps of pyrolysis and/or solvent extraction, recycle streams andseparations. From a process and method perspective, the solventextraction and pyrolysis steps are integrated. The primary processingstep 100 generates at least one solid output and liquid output, but maygenerate multiple solid and liquid output streams based on theconfiguration of the primary processing step 100. In some cases, liquidswill undergo additional liquid processing 102, with the option of liquidrecycle streams 106 returning specific liquid fractions to the primaryprocessing 100. In some cases, liquid recycle streams 106 includingsolvent recycle streams may be useful as intermediates to downstreamprocesses or as products and may be separately sold or processed.Similarly, solids may under additional solid processing 104, withoptional recycle streams 104. The end result is at least one high valueliquid product and at least one high value solid product, althoughtypically the described processes will generate a variety of high valueproducts as well as lower value products (relative to feedstock cost)which may or may not be re-processed or sold.

An example of the processing step 100 is provided in FIG. 2. First, thecoal-based feedstock is treated via pyrolysis 200 reduce carbon chainlength and liquefy or vaporize a portion of the feedstock. In thisexample, pyrolysis is performed at 400-1200° C. and at atmosphericpressure. Flash pyrolysis (e.g. resonance time of less than 1 minute) orpyrolysis with low resonance times (e.g. less than 15 minutes) may beused to increase efficiency, change product make and yields and/ordecrease processing time while reducing energy requirements and,therefore, costs. The fluids from the pyrolysis process 200 may beeither further processed (e.g. separated, polymerized, etc.) indownstream operations. The solids from the pyrolysis process 200 aresent to a solvent extraction unit 210. Solvent extraction 210 furtherremoves fluid components from the solid materials and may provide somechemical reaction such as reducing carbon chain length, increasing theratio of hydrogen/carbon or interacting with sulfur and oxygen bonds andrecovery of metals and rare earth elements. Remaining solids from thesolvent extraction step 210 may be further treated as described herein,recycled through the process for additional conversion into lightercompounds or converted into other high value products. The fluid streamfrom the solvent extractor 210 may be separated, for example, in adistillation column 220. The fluid stream may be split into one or moreproduct streams based on volatility and solvent may be recovered andreturned to the solvent extractor 210. FIG. 8 provides additionalexamples of integrated, multistage processing steps and furtherillustrates the versatility in ordering of the various process steps.

Example 2—Pyrolysis

Pyrolysis used in the described systems and methods provides for thethermal decomposition of complex hydrocarbons found in coal and helpsconvert a portion of the solid coal materials into liquids and vapors.Pyrolysis as described herein is generally performed at a hightemperature while being low enough to avoid combustion, for example,greater than 400° C., greater than 800° C., or optionally, greater than1000° C. Further, to increase efficiency and reduce energy costs,pyrolysis of the described methods has generally low residence times,for example, less than 1 hour or in some cases less than 15 minutes.Some embodiments of the present invention utilize flash pyrolysis whichmay have a residence time less than 1 minute, or preferably less than 15seconds. The described pyrolysis steps may be performed at or nearatmospheric pressure or in a pressurized environment, including in someembodiments, in the presence of a hydrogen-rich gas including hydrogengas, methane, natural gas or syngas.

Specific pyrolysis parameters are dependent on the input or feed stream.For example, in embodiments where pyrolysis is the first step in thedescribed methods, the feed will be primarily coal or coal-derivedmaterial. However, in cases in which one or more solvent extractions areperformed, the remaining solid material may have significantly differentcompositions and process parameters will need to be altered accordingly.

Coal pyrolysis experiments were performed on Cordero Rojo sub-bituminouscoal. 25 g of coal was dried overnight at 100° C. under argon. The drycoal weight was determined and this becomes the basis for the yieldcalculations below. Then the contents were heated to 500° C. in avertical tube furnace for 40 minutes. The generated pyrolysis vaporswere sent to a cold trap at 0° C. to condense the tars and vent theremaining gas.

Below are weight-based yield results for dry coal based on theexperimental procedure above:

TABLE 1 Weight-based yield results for pyrolysis Yield % Notes SolidChar 79.1 Char Weight * 100 Yield % Dry Coal Weight Tar (liquid) 10.5Cold Trap Liquid Tar Weight * 100 Yield % Dry Coal Weight Gas Yield %10.4 By difference

Example 3—Solvent Extraction

Solvent extraction provides an effective, cost efficient way to recoverdesirable and valuable fluid components from a predominately solidfeedstock or intermediate. Additionally, selection and design ofsolvents may provide some chemical reactivity and may reduce the size orlength of the complex hydrocarbon molecules often found in coal and orpermit the economic recovery of metals and rare earth elements.

A variety of solvents are useful for the treatment of coal-basedfeedstocks or intermediate coal products (e.g. post-pyrolysis). Polarsolvents, hydrogen donating solvents, aliphatic solvents, aromaticsolvents, ionic liquid solvents and supercritical fluid extraction(including other solvents) all allow for high flexibility in promotingthe production of certain products or product types and changes insolvent systems or processes parameters can account for differencesbetween various coal feedstocks and types. The temperature and pressureof solvent extraction is often tied to the solvent being used, but bothsubcritical and supercritical solvent extraction may be implemented.

Multiple solvent extractions with different solvent systems and/orprocess parameters allows for higher efficiency in converting solidmaterial into more easily processed and potentially more valuable fluidoutputs. An example of multiple single stage solvent extractions isprovided in FIG. 3. A feed 201 (which may be a coal-based feedstock, apyrolysis product or an intermediate that has undergone multiple processsteps, including both pyrolysis and solvent extraction) is provided intoa first solvent extractor 210. The solvent extractor 210 uses a specificsolvent type, for example, a polar solvent to target certain coalcomponents such as aromatics. The first extract is then split in one ormore separation steps 220, such as a distillation column, resulting inboth a light fluid output and a heavy fluid output. Solvent may berecycled back into the solvent extractor 210. The solids remaining afterthe solvent extraction 210 are then processed in a second solventextraction process 211 that uses a different solvent type, for example ahydrogen donating solvent, to extract additional fluids remaining in thesolids. Importantly, the order of solvent extraction processes may bereversed or altered to increase the quantity of certain hydrocarbonsallowing for diverse product selection. The extract from the secondsolvent extraction 211 is also fed to a separation step or steps 221,providing both a light and heavy fluid output and the ability to recyclesolvent. Solids remaining after the multistage solvent extraction may befurther processed (e.g. pyrolysis or additional solvent extraction) ormay be processed as solid products as described herein.

Multistep solvent extractions, wherein a single solvent is appliedmultiple times to increase total extraction, and fractionation, whereina single solvent is applied at different temperatures may also beutilized in some embodiments.

Solvent extraction experiments were performed to examine the extractionefficiency of tetralin and 1-methyl-naphthalene with Cordero Rojosub-bituminous coal (the same coal as described in Example 2 and Table1). The experimental procedure was to dry coal for 36 hours at 90° C.under a flowing argon stream; this resulted in coal having <1% (wt)moisture. After drying, the dry coal is weighed and this becomes thebasis for the yield calculations below, assuming 0% moisture.Approximately 100 g of coal was placed in a pressure vessel which wasthen placed in an oven. The desired solvent is pumped at a rate of 0.1ml/g dry coal per minute and to a pressure above the boiling point atthe desired temperature. The oven is turned on and the vessel is heatedto a controlled 360° C. The solvent flow continues for 2 hrs after thistemperature is reached. Insignificant (assumed zero) gas flows werenoted. After 2 hrs, the solvent flow is stopped and the oven turned off,thus allowing the vessel to cool. The pressure drops to atmospheric.After cooling to below the boiling point of the solvent, argon is flowedthrough the vessel for 36 hrs to remove remaining solvent from the solidresidue. The resulting residue is weighed to determine the yield.

Below are weight-based yield results for dry coal based on theexperimental procedure above:

TABLE 2 Weight-based yield results for solvent extraction 1-Methyl-Solvent Tetralin Naphthalene Notes Solid Residue 53.3% 71.2% ResidueWeight * 100 Yield % Dry Coal Weight Extract Yield % 46.7% 28.8% Bydifference; solvent free basis

Example 4—Integrated Thermochemical Processing

The solids collected from the pyrolysis (Example 2) and the solventextraction (Example 3) experiments were then subjected to the secondprocessing option. In other words, solvent extraction solid residue waspyrolyzed and pyrolysis char was solvent extracted. Refer to FIGS. 1, 2and 8.

The solvent extraction experimental procedure and conditions were thesame as described in the Solvent Extraction (Example) except that nodrying was required.

The pyrolysis experimental procedure and conditions were the same asdescribed in the Pyrolysis Example except that no drying was required.

Below are weight-based tetralin solvent extraction yield results for drypyrolysis char based on the experimental procedure above:

TABLE 3 Weight-based yield results for pyrolysis followed by solventextraction Solvent Tetralin Notes Solid Residue 97% Residue Weight * 100Yield % Dry Char Weight Extract Yield %  3% By difference; solvent freebasis

Below are weight-based pyrolysis yield results for dry tetralin-basedsolvent extraction residue based on the experimental procedure above:

TABLE 4 Weight-based yield results for solvent extraction followed bypyrolysis Yield % Notes Solid Char 86.1% Char Weight * 100 Yield % DrySolvent Residue Weight Tar (liquid) 5.5% Cold Trap Liquid Tar Weight *100 Yield % Dry Solvent Residue Weight Gas Yield % 8.4% By difference

Below are the combined 2-step process overall weight-based yield resultsbased on the results above plus results from coal pyrolysis and coalsolvent extraction examples. The solvent used was tetralin.

TABLE 5 Weight-based yield results comparison Solvent Extraction thenPyrolysis then Solvent Pyrolysis Yield % Extraction Yield % Solid Char46 77 Yield % Tar + Extract 50 13 (liquid) Yield % Gas Yield % 4 10

It should be noted that in both cases the tar yields from a two-stepprocess is greater than from pyrolysis-only or solvent extraction-onlyprocesses.

Example 5—Branching Processes

By including additional processing steps, including steps after thecombination of pyrolysis and solvent extraction produces a highlybranched process which can result in a range of products yielded ordifferent specifications and functionality for the same family ofproduct types made. These additional processes convert intermediateproducts resulting from thermochemical treatment (noted in FIG. 2). Thefinal product manufacturing processes (formulations) which are fed byintermediates provide high-selectivity an ability to make amounts ofproduct that exhibit performance that ensure economic stability withadjustments to product flows and conditions that permit meetingproduct-based market demand.

FIG. 9 provides an example of a highly branched, highly selectiveprocess with additional post processing to generate various high-valueand useful products. The described process consists of 3 stages whichare integrated: thermal and chemical decomposition, vapor-liquidseparations, and product manufacture/formulation which can be a singledirect process or the production of an intermediate product beforefurther processing to make the high value derivative or end product.

The thermal and chemical decomposition section consists of a minimum of2 processing steps, pyrolysis and solvent extraction, with the possibleaddition of further post treatment steps, which are performed in series.This process provide the maximum liquid intermediate yields (from theseparations section) which are the primary feeds to vapor-liquid productmanufacturing or formulations. The thermal and chemical decompositionstep consists of pyrolysis followed by solvent extraction of thepyrolysis char or of solvent extraction of the primary feedstockfollowed by pyrolysis of the solvent extraction solid residue. Pyrolysisis the direct or indirect heating of primary feedstock or solventextraction residue, in a neutral or hydrogen-donor atmosphere (such ashydrogen-rich gas, syngas, or methane). Gas and solid products resultfrom pyrolysis. Solvent extraction consists of contacting the primaryfeedstock or coal-pyrolysis char which can be multiple steps and withdifferent solvents. Solvents are recovered in the separations sectionand a solvent-rich stream recycled to solvent extraction. Solventcarried over into the next processing step is minimized. Solventextraction produces little gas, operates at temperatures below pyrolysistemperatures, and produces a solvent containing extract liquid streamand a solid residue stream. FIG. 8 illustrates the integrated thermaland chemical decomposition step.

The separations section processes the vapor and liquid intermediatesfrom the thermal and chemical decomposition section to makeintermediates which feed for the product formulations section. Dependingupon the type of atmosphere in the pyrolysis reactor, gases from theseparations section may be processed and recycled to the pyrolysisreactor. A solvent-rich stream will be recovered in the separationssection and recycled to the solvent extraction section or used as anintermediate product for further processing into a finished product. Theseparations section will depend upon both the conversion section(temperature, pressure, processing order, pyrolysis atmosphere, andsolvent scheme) and the product formulation sections. Pyrolysis vaporsand solvent extraction extract may be combined to feed a singleseparations section or they may feed separate, parallel separationsections, depending upon which high-value products are deliberatelyselected and which will be byproducts or co-products. A distillationtower may be the first unit operation in the separations section toremove gaseous products from the thermal and chemical decompositionsection and produce various liquid intermediate. Side strippers and sideabsorbers may be present. The bottoms (residue products) from this firsttower will be capable of being sent to a high-vacuum distillation towerto further refine the heaviest material. Depending upon productformulations specifics, the liquid intermediates may be furtherseparated or processed to produce a desired intermediate feed for aspecific product formulation. These downstream separations could consistof adsorption, fractionation, crystallization, azeotropic fractionation,extractive distillation, liquid-liquid decanting and extraction,including combinations of these. Unused (for product formulations)intermediates (for example, intermediates with a higher boiling pointrange) may be recycled to the thermal and chemical decomposition sectionto further process this material into a more usable intermediates.

Product formulations consists of two main sub-sections: intermediate(liquid) and gas product formulations and solids, which are processed inpost treatment formulations to make final products. The finalformulations will process the intermediates from the separations sectionto produce 2-10 high-value products and possibly additional lower-valueproducts. Examples of these high-value products can be petrochemicals,carbon fibers, polymers, composites, asphaltenes, binders, coke, andothers. Each of these high-value products will be produced in a separateprocessing unit using a customized feed from the separations section.The solids from the thermal and chemical decomposition section will besent to solids formulations. Again, several products will be made inseparate processing units. Examples of lower value products includewater, minerals and clays together with flue gas. Examples of high valueproduct extracts include metals and rare earth elements.

The processes described herein are somewhat analogous to a crude oilrefinery, which is fed crude oil and where there are multiple conversionsteps, many separations (especially fractionation) steps, manyintermediates produced, and a multitude of derivative products,generally made using distillation as a primary process step to makeintermediates followed by discrete hydrocracking, hydrotreating andhydroprocessing to make finished products. However, the describedprocesses herein are specifically tailored for a solid, high carboncontent feedstock requiring a distinct and unique integration ofthermochemical processes, and which generate a significant volume ofsolid high value products, liquid products which either technically oreconomically or both cannot be derived in a petroleum refinery andconversely generates a small volume of fuel products and/or fuelblending components.

FIGS. 5-7 provide more detailed examples of potential processintegrations to provide specific examples of high value products. InFIG. 7, a coal based feed stock in placed into a dryer to remove about90% of water content. Next, the dried coal is converted in thethermochemical processing step, in this example consisting of twosolvent extraction steps and a single pyrolysis step which are fullyintegrated. The first solvent extraction utilizes a polar solvent (e.g.DMF, ethanol, water) to recover oxygen containing molecules. The secondsolvent extraction uses a non-polar solvent (e.g. mixed hydrogenatedoils, tetralin, supercritical fuels, 1-methyl-naphthalene). Pyrolysis ofthe solvent extraction residue is performed at 400-1200° F. to producesoil amendment products and building materials together with valuablehydrocarbon containing vapors as intermediates for further processing.

After thermochemical processing, the various streams are separated byknown techniques including, for example, distillation, vacuumdistillation, solvent extraction, crystallization, wipe-filmevaporation, liquid-liquid extraction and decanting. In someembodiments, products which are separated may be recycled to thethermochemical processing step until a desired composition, conversionor boiling point range has been achieved. In some cases, separations maybe performed between thermochemical processing steps (i.e. solventextraction 1-separations-pyrolysis-solvent extraction 2). For tarstreams, vacuum distillation may be used to generate various productsbased on the boiling point of the stream. Fuel gasses coming off theseparations step(s) may be processed in a gas clean up step, such asamine treatments, scrubbing or membrane filtering to remove undesirablegases (e.g. carbon dioxide and SOx and NOx pollutants). After cleaning,fuel gases may also be further converted using dry methane reforming(DMR) or steam methane reforming (SMR) and deployed in the processingsteps or sold.

Solid products from the thermochemical processing steps may beformulated into finished products or used as intermediates from whichfinished products can be manufactured or sold. Examples products includecarbon filler byproduct for building materials, further processing toproduce activated-carbon products for environmental management or usedto make soil amendments or further calcined to produce coke.

Example 6—Branching from Thermochemical Coal Processing

With reference to FIGS. 5 and 6 and this Example demonstrates howthermochemical processing of coal can be adapted and is flexible toproduce a multitude of distinctive product manufacturing outcomes basedupon the unique integrated and synergistic operation of thethermochemical process defined herein. The examples describe laboratoryscale experiments that demonstrate proof of concept and viability ofadditional conversion of coal based materials into high demand and highvalue products.

Coal Exfoliates

Described are coal solids from which polar and non-polar molecules havebeen extracted with highly exfoliated properties and high surface areaform, which may be used as soil remediation additives, gas/fluidabsorbents, graphene oxide spray slurries, and chars for gasificationand hydrogenation.

Experimentally, a two-step experimental process including: 1) Removal ofpolar molecules via a continuous extraction using DMF at 140° C. @1 atmand 2) Removal of non-polar molecules via supercritical CO₂ extractionat 40° C. @ 75 atm. The two steps can be applied in any order.

Room Temperature Urethane Foam Composite Synthesis

Described are organic composite materials consisting of an organicmatrix filled with reinforcing particles with sufficient structuralstrength to act as fillers in skin/matrix structural composites or asfreestanding foams for acoustic modulation, thermal insulation,ballistic impact mitigation or buoyancy. These coal based functionalizedcarbon particles together with a coal derived urethane matrix mayproduce a low cost polymeric matrix composite (PMC) with highlydesirable properties.

Described herein is a process that produces urethane composites fromorganic coal extracts without intermediate separation of the extractinto its individual chemical or boiling point range constituents, byreacting two solutions at room temperature to form a durable foam withsignificantly greater volume in a matter of minutes. This processrequires no caustic or dangerous reagents during the foam synthesis stepand uses the alcoholic/phenolic OH groups on the extract and reacts themin standard fashion with a di-isocyanate cross-linking agents to producea non-differentiated poly-urethane having good thermal capability aswell as reasonable toughness, tensile strength and elasticity. Thisprocess also takes advantage of the alcoholic/phenolic OH groups ongraphene oxide produced from coal via the Hummer's method or graphiticcoal char produced from coal. The addition of graphene oxide orgraphitic coal char would greatly increase the strength of the coal PMC.

Experimentally produced coal extract is made in a continuous Soxhletprocess using a standard evaporator, condenser and filter/syphon schemewith dimethylformamide as the solvent. A portion of the coal extract isthen pyrolysed at 850° C. for 10-15 minutes in wet air and then crushedto a 200-mesh size. As a laboratory example, graphene oxide is producedvia the standard Hummer's method from coal. A mixture of 0.5 g of waterand 1% (w/w %) graphene oxide or 1% (w/w %) graphitic coal char, 0.1 gof dibutyltin dilaurate and 2 g of the coal extract is be prepared.Approximately 14 g of toluene d-isocyanate is added to the mixture andstirred by hand vigorously, which causes the solution to foam, afterwhich is allowed to cool to room temperature.

Production of Polyamides from Coal

Described is a process that produces polyamides from organic coalextracts without intermediate separation of the extract into itsindividual chemical or boiling point range constituents. This processtakes advantage of the carboxylic acid groups on the extract and reactsthem in standard fashion with a diamine cross-linking agents to producea non-differentiated polyamides having good thermal capability as wellas reasonable toughness, tensile strength and elasticity.

Coal extract is made by suspending coal in a high temperature, highpressure tetralin. The dissolved extract precipitates from solution asthe temperature and pressure is reduced. As a laboratory scale example,0.5 g of the solid extract is then dissolved in DMF and heated underreflux at 130° C. for 4 hours with a 0.5 g of hexamethylene diamine. Thesolution is then placed in a heated petri dish and the DMF evaporated toproduce deposits of the polyamide.

A second sample of polyamide is made by suspending 10 g coal indimethylformamide at room temperature. This dissolved extract isseparated by filtration from the solids and then directly reacted with0.5 g of hexamethylene diamine at 150° C. and 1 atmosphere pressure. Thesolution was refluxed for 4 hours and placed in a heated petri dish toform the polyamide deposit as above.

By varying chemical composition, reaction conditions and solventsystems, engineered polyamides can be produced that have differentphysical, chemical and intrinsic properties, like flexibility, tensilestrength, glass transition temperature of the resulting polymer.

Conductive Composite Derived from Coal

There is a current technical need for organic composite materials whichhave sufficient electrical conductivity to shield the electromagneticemission coming from computer CPU's, cell phones, microwave ovens andthe like. High cost thermoplastics filled with moderate cost carbonblack is commonly used, but the market is looking for fillers withhigher conductivity at lower fill volume. Graphene and multi or singlewalled carbon nanotubes function perfectly in this role; however, theirhigh price prevents them from achieving widespread use. A coal basedcarbon particle with a prolate or oblate shape may achieve a lowervolume fill in an electrically conductive composite at a significantlylower price.

Described is a three step process to make an electrically conductiveorganic composite system consisting of a coal based derived polymericmatrix composite (PMC) that utilizes a coal based polymeric base with asecond, coal based, carbon filler to form an electrically conductivecomposite.

The process scheme consists of 3 stages, namely 1) Extraction of organicresidue, 2) Conversion of resulting solid to functionalized graphiticchar, and 3) Reacting the residue and functionalized char with adi-isocyanate to make a urethane based polymeric composite.

Experimentally, the coal residue is extracted using DMF as a solvent attemperatures up to 450° C. where temperatures over 150° C. require apressure vessel with increased volume of extract yield attainable withincreasing temperature. This solution is then used in making thecomposite. The solids remaining after the residue extraction arepyrolysed at 850° C. for 10-15 minutes and the char is then ground to a200-mesh size and further ground on a ball mill with ethanol added as acarrier fluid. After milling for 16 hours, the char is filtered toremove the solvent and then placed in a stainless steel bomblet with1/10 equivalent weights of a di-isocyanate. The bomblet is sealed andheated to 400° C. to functionalize the char. The char is then washedwith several aliquots of acetone to remove the excess di-isocyanate anddried.

Polyesters Derived from Coal

Described is a process that produces polyesters from organic coalextracts without intermediate separation of the extract into itsindividual chemical constituents. This process takes advantage of thecarboxylic acid groups on the extract and reacts them in standardfashion with a diol cross-linking agents to produce a non-differentiatedpolyesters having good thermal capability as well as reasonabletoughness, tensile strength and elasticity.

Coal extract is made by suspending coal in a high temperature, highpressure tetralin. The dissolved extract precipitates from solution asthe temperature and pressure are reduced. Experimentally, 0.5 g of thesolid extract is dissolved in DMF and heated under reflux at 130° C. for4 hours with a 0.35 g of ethylene glycol. The solution is then placed ina heated petri dish and the DMF evaporated to produce deposits of thepolyester.

A second sample of urethane is made by suspending 10 g coal indimethylformamide at room temperature and the extract is separated byfiltration from the solids and then directly reacted with 0.35 g ofethylene glycol at 150° C. and 1 atmosphere pressure. The solution wasrefluxed for 4 hours and placed in a heated petri dish to form thepolyester deposit as above.

To control desirable properties, substitution of other glycols such aspropylene glycol, benzenediol, or bisphenol may result in a similarpolymer and that in combination with mixtures of diols can be used tocontrol desirable properties, like flexibility, tensile strength, glasstransition temperate, of the resulting polymer.

Structural Foam Composite

Described is a multi-step process, including: 1) Liquid Extraction ofpolar organic residue from low rank coals, 2) Distillation or otherseparation of the polar extract to recover high volatile organics andtoluene and other selected aromatics, 3) Conversion of these remainingaromatics to di-isocyanates via acidic nitration followed byhydrogenation, followed by phosgene carboxylation, 4) Conversion of theremaining solid to functionalized graphitic char and 5) Reacting theresidue, the di-isocyanate and functionalized char to make a urethanebased polymeric composite.

The coal residue is extracted using DMF as a solvent at temperatures upto 450° C. where temperatures over 150° C. require a pressure vessel andthe volume yield of extract increases with temperature. Prior toreacting to form the composite, the concentration of residue in thesolvent should approach 1 g residue/2 g solvent. i.e. as close tosaturation as possible. This solution is used to make the composite.

Toluene is nitrated in a HNO₃/H₂SO₄ solution and the di-nitratehydrogenated to the di-amine with hydrogen at 500° C. in a pressurevessel. The diamine is converted to di-isocyanante by exposure tophosgene at 250° C.

The solids remaining after the residue extraction are then pyrolysed at850° C. for 10-15 minutes in wet air and then crushed to a 200-meshsize. This powder is further ground on a ball mill with ethanol added asa carrier fluid. After milling for 16 hours, the char is filtered toremove the solvent and then placed in a stainless steel bomblet withequal weight of extracted residue and equal (residue+char) weight of thedi-isocyanate. The bomblet is sealed and heated to 180° C. to form thecomposite.

The resulting foam had a density of 0.33 g/cc and a crush strength>150PSI.

Urethanes from Coal

Described is a process that produces urethanes from organic coalextracts without intermediate separation of the extract into itsindividual chemical constituents. This process reacts alcoholic/phenolicOH groups on the extract a with a di-isocyanate cross-linking agents toproduce a non-differentiated polyurethane having good thermal capabilityas well as reasonable toughness, tensile strength and elasticity.

Experimentally, coal extract was made by suspending coal in a hightemperature, high pressure tetralin solution, whereby the dissolvedextract precipitated from solution as the temperature and pressure werereduced. Experimentally, 0.5 g of the solid extract is then dissolved inacetone and heated under reflux at 60° C. for 4 hours with a 0.25 g oftoluene di-isocyanate. The solution is then placed in a heated petridish and the acetone evaporated to produce films of the urethane. Asecond sample of urethane is made by suspending 10 g coal indimethylformamide at room temperature. This dissolved the extract isseparated by filtration from the solids and then directly reacted with0.5 g of toluene di-isocyanate at 150° C. and 1 atmosphere pressure. Thesolution is refluxed for 4 hours and placed in a heated petri dish toform the urethane film as above.

A third sample is made identically to sample 2 with the exception that 2drops of di-butyl tin dilaurate is added to the isocyanate mixture as acatalyst and the solution is refluxed for only 1 hour prior to placingin a dish to evaporate the solvent.

Substitution of other di-isocyanates such as 1,6-diisocyanato hexane mayresult in a similar polymer and that mixtures of isocyanates can be usedto control desirable properties, like flexibility, tensile strength,glass transition temperate, of the resulting polymer.

Graphene/Graphene Oxide Films and Powders Derived from Coal

Described is a multi-step process for the synthesis of graphene powdersand films from coal as well as outlining a pathway to synthesizegraphite oxide powders and reduced graphene oxide films from coal. Theprocess includes: 1) Volatile burn off of organic material from coal for30 minutes at 850° C. and 2) High temperature graphitization in aninert, vacuum environment of resulting solids via induction heating(>2500° C.) of a graphite crucible that contains the resulting solidfrom step 1.

The graphene powder or film is then produced by: 3) Tip/bath sonicationof resulting material in spray friendly solvents (ethanol and isopropylalcohol), 4) Centrifugation of the material to select nanoflake materialin supernatant followed by decanting of solution to remove the bottomsolid material, 5) Vacuum drying of the supernatant produces grapheneflake powder (powder synthesis), 6) Forced nebulization of supernatantfrom step 4 onto heated substrates to form conductive films of variablethickness and conductivities, and 7) Synthesized films were then furtherannealed via tube furnace annealing from 800-1450° C. (Film synthesis).

Alternatively, graphite oxide powder and graphene oxide films may beproduced via: 3) Oxidation of material using strong oxidizer forvariable time or until violent oxidation of solution occurs. Theoxidizing solution consisted of 98% sulfuric acid, potassiumpermanganate, and sodium nitrate, 4) The solids are collected viacentrifugation and washed 3× with deionized water with each washfollowed by centrifugation and 5) The solution supernatant was discardedand the solids dried via freeze drying (Powder synthesis).

Example 7—Proximate and Ultimate Analysis

Analysis of Pyrolysis Char

Sample ID: CE-16-Pc (Char)

TABLE 6 Proximate and Ultimate Analysis of Pyrolysis Char (Refer toExample 2, Table 1) As Received Moisture Moisture & Ash ASTM wt % Freewt % Free wt % Method Proximate Analysis Moisture 1.55 ***** ***** D7582Ash 11.46 11.64 ***** D7582 Volatile 24.98 25.37 28.71 D7582 MatterFixed Carbon 62.02 62.99 71.29 calculated Total 100.00 100.00 100.00Ultimate Analysis Moisture 1.55 ***** ***** D7582 Ash 11.46 11.64 *****D7582 Carbon 73.89 75.05 84.93 D5373 Hydrogen 3.34 3.39 3.83 D5373Nitrogen 3.87 3.93 4.45 D5373 Sulfur 0.45 0.46 0.52 D4239 Oxygen 5.455.53 6.26 calculated Total 100.00 100.00 100.00 As Received MoistureMoisture & Ash ASTM Btu/lb Free Btu/lb Free Btu/lb Method Heating 12,23712,430 14,067 D5865 Value

Hydrogen and Oxygen values reported do not include hydrogen and oxygenin the free moisture associated with sample. Reported results calculatedby ASTM D3180. Results are an average of 2 runs.

Analysis of Pyrolysis Char Form the Pyrolyzed Residue of the SolventExtracted Coal

Sample ID: CE-13-Res-Pc (Char)

TABLE 7 Proximate and Ultimate Analysis of Pyrolysis Char wherepyrolysis occurred post solvent extraction (Refer to Example 4, Table 4)As Received Moisture Moisture & Ash ASTM wt % Free wt % Free wt % MethodProximate Analysis Moisture 1.07 ***** ***** D7582 Ash 13.22 13.36 *****D7582 Volatile 25.59 25.87 29.86 D7582 Matter Fixed Carbon 60.11 60.7770.14 calculated Total 100.00 100.00 100.00 Ultimate Analysis Moisture1.07 ***** ***** D7582 Ash 13.22 13.36 ***** D7582 Carbon 70.81 71.5882.63 D5373 Hydrogen 3.41 3.45 3.98 D5373 Nitrogen 1.27 1.29 1.49 D5373Sulfur 0.21 0.21 0.24 D4239 Oxygen 10.00 10.11 11.67 calculated Total100.00 100.00 100.00 As Received Moisture Moisture & Ash ASTM Btu/lbFree Btu/lb Free Btu/lb Method Heating 11,549 11,674 13,475 D5865 Value

Hydrogen and Oxygen values reported do not include hydrogen and oxygenin the free moisture associated with sample. Reported results calculatedby ASTM D3180. Results are an average of 2 runs.

Analysis of Residue from the Solvent Extraction of the Pyrolysis CharTested in Table 6

Sample ID: CE-16-Res

TABLE 8 Proximate and Ultimate Analysis of solvent extraction residue ofthe sample (CE-16-Res) tested in Table 6 (Refer to Example 4, Table 3)As Received Moisture Moisture & Ash ASTM wt % Free wt % Free wt % MethodProximate Analysis Moisture 0.50 ***** ***** D7582 Ash 10.11 10.16 *****D7582 Volatile 23.59 23.70 26.38 D7582 Matter Fixed Carbon 65.81 66.1473.62 calculated Total 100.00 100.00 100.00 Ultimate Analysis Moisture0.50 ***** ***** D7582 Ash 10.11 10.16 ***** D7582 Carbon 75.25 75.6384.18 D5373 Hydrogen 3.69 3.71 4.13 D5373 Nitrogen 1.41 1.41 1.57 D5373Sulfur 0.34 0.34 0.38 D4239 Oxygen 8.71 8.75 9.74 calculated Total100.00 100.00 100.00 As Received Moisture Moisture & Ash ASTM Btu/lbFree Btu/lb Free Btu/lb Method Heating 12,572 12,635 14,063 D5865 Value

Hydrogen and Oxygen values reported do not include hydrogen and oxygenin the free moisture associated with sample. Reported results calculatedby ASTM D3180. Results are an average of 2 runs.

TABLE 9 Quality Control Reference % Parameter Material Expected ResultRecovery Ash AR2775 6.80 6.32 93 Volatile Matter AR2775 37.77 39.6 105Carbon hs-10006a 65.6 63.64 97 Hydrogen hs-10006a 6.69 6.72 100 Nitrogenhs-10006a 8.2 8.45 103 Sulfur AR1701 0.53 0.55 104 Heating Value, Benz 111,373 11,413 100 Btu/lb

STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and “at least one” andsimilar referents in the context of describing the invention (especiallyin the context of the following claims) are to be construed to coverboth the singular and the plural, unless otherwise indicated herein orclearly contradicted by context. The use of the term “at least one”followed by a list of one or more items (for example, “at least one of Aand B”) is to be construed to mean one item selected from the listeditems (A or B) or any combination of two or more of the listed items (Aand B), unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

All references throughout this application, for example patent documentsincluding issued or granted patents or equivalents; patent applicationpublications; and non-patent literature documents or other sourcematerial; are hereby incorporated by reference herein in theirentireties, as though individually incorporated by reference, to theextent each reference is at least partially not inconsistent with thedisclosure in this application (for example, a reference that ispartially inconsistent is incorporated by reference except for thepartially inconsistent portion of the reference).

The terms and expressions which have been employed herein are used asterms of description and not of limitation, and there is no intention inthe use of such terms and expressions of excluding any equivalents ofthe features shown and described or portions thereof, but it isrecognized that various modifications are possible within the scope ofthe invention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments, exemplary embodiments and optional features, modificationand variation of the concepts herein disclosed may be resorted to bythose skilled in the art, and that such modifications and variations areconsidered to be within the scope of this invention as defined by theappended claims. The specific embodiments provided herein are examplesof useful embodiments of the present invention and it will be apparentto one skilled in the art that the present invention may be carried outusing a large number of variations of the devices, device components,methods steps set forth in the present description. As will be obviousto one of skill in the art, methods and devices useful for the presentmethods can include a large number of optional composition andprocessing elements and steps.

When a group of substituents is disclosed herein, it is understood thatall individual members of that group and all subgroups, including anyisomers, are disclosed separately. When a Markush group or othergrouping is used herein, all individual members of the group and allcombinations and subcombinations possible of the group are intended tobe individually included in the disclosure. When a compound is describedherein such that a particular isomer of the compound is not specified,for example, in a formula or in a chemical name, that description isintended to include each isomers of the compound described individual orin any combination. Additionally, unless otherwise specified, allisotopic variants of compounds disclosed herein are intended to beencompassed by the disclosure. For example, it will be understood thatany one or more hydrogens in a molecule disclosed can be replaced withdeuterium or tritium. Isotopic variants of a molecule are generallyuseful as standards in assays for the molecule and in chemical andbiological research related to the molecule or its use. Methods formaking such isotopic variants are known in the art. Specific names ofcompounds are intended to be exemplary, as it is known that one ofordinary skill in the art can name the same compounds differently.

Many of the molecules disclosed herein contain one or more ionizablegroups [groups from which a proton can be removed (e.g., —COOH) or added(e.g., amines) or which can be quaternized (e.g., amines)]. All possibleionic forms of such molecules and salts thereof are intended to beincluded individually in the disclosure herein. With regard to salts ofthe compounds herein, one of ordinary skill in the art can select fromamong a wide variety of available counterions those that are appropriatefor preparation of salts of this invention for a given application. Inspecific applications, the selection of a given anion or cation forpreparation of a salt may result in increased or decreased solubility ofthat salt.

Every formulation or combination of components described or exemplifiedherein can be used to practice the invention, unless otherwise stated.

Whenever a range is given in the specification, for example, atemperature range, a pressure range, a time range or a composition orconcentration range, all intermediate ranges and subranges, as well asall individual values included in the ranges given are intended to beincluded in the disclosure. It will be understood that any subranges orindividual values in a range or subrange that are included in thedescription herein can be excluded from the claims herein.

All patents and publications mentioned in the specification areindicative of the levels of skill of those skilled in the art to whichthe invention pertains. References cited herein are incorporated byreference herein in their entirety to indicate the state of the art asof their publication or filing date and it is intended that thisinformation can be employed herein, if needed, to exclude specificembodiments that are in the prior art. For example, when composition ofmatter are claimed, it should be understood that compounds known andavailable in the art prior to Applicant's invention, including compoundsfor which an enabling disclosure is provided in the references citedherein, are not intended to be included in the composition of matterclaims herein.

As used herein, “comprising” is synonymous with “including,”“containing,” or “characterized by,” and is inclusive or open-ended anddoes not exclude additional, unrecited elements or method steps. As usedherein, “consisting of” excludes any element, step, or ingredient notspecified in the claim element. As used herein, “consisting essentiallyof” does not exclude materials or steps that do not materially affectthe basic and novel characteristics of the claim. In each instanceherein any of the terms “comprising”, “consisting essentially of” and“consisting of” may be replaced with either of the other two terms. Theinvention illustratively described herein suitably may be practiced inthe absence of any element or elements, limitation or limitations whichis not specifically disclosed herein.

One of ordinary skill in the art will appreciate that startingmaterials, biological materials, reagents, synthetic methods,purification methods, analytical methods, assay methods, and biologicalmethods other than those specifically exemplified can be employed in thepractice of the invention without resort to undue experimentation. Allart-known functional equivalents, of any such materials and methods areintended to be included in this invention. The terms and expressionswhich have been employed are used as terms of description and not oflimitation, and there is no intention that in the use of such terms andexpressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the invention claimed.Thus, it should be understood that although the present invention hasbeen specifically disclosed by preferred embodiments and optionalfeatures, modification and variation of the concepts herein disclosedmay be resorted to by those skilled in the art, and that suchmodifications and variations are considered to be within the scope ofthis invention as defined by the appended claims.

We claim:
 1. A method for converting coal into a plurality of high valuecoal products and extracts comprising: providing a feedstock, whereinsaid feedstock is at least partially derived from coal; processing saidfeedstock, wherein said processing step includes a combination ofpyrolysis and solvent extraction, wherein said pyrolysis and solventextraction are integrated and carried out under conditions forgenerating a plurality of high value coal products.
 2. The method ofclaim 1, wherein greater than or equal to 50% by mass dry basis of saidhigh value coal products are liquid at standard temperature andpressure.
 3. The method of claim 1 or 2, wherein said step of processingsaid step is highly branched and highly selective.
 4. The method of anyof claims 1-3, wherein said pyrolysis is performed at a pressureselected from the range of 0.5 atm to 15 atm.
 5. The method of any ofclaims 1-4, wherein said pyrolysis is performed at a temperatureselected from the range of 400° C. to 1200° C.
 6. The method of any ofclaims 1-5, wherein said pyrolysis is performed in less than or equal to5 seconds.
 7. The method of any of claims 1-6, wherein said pyrolysis isintegrated with said solvent extraction.
 8. The method of any of claims1-7, wherein said pyrolysis generates a mass percentage of gas of lessthan or equal to 25%, excluding water vapor.
 9. The method of any ofclaims 1-8, wherein said pyrolysis is performed in the presence ofhydrogen gas, methane, syngas or any combination thereof.
 10. The methodof any of claims 1-9, wherein said pyrolysis is flash pyrolysis.
 11. Themethod of any of claims 1-10, wherein said solvent extraction isperformed with at least one liquid solvent.
 12. The method of any ofclaims 1-11, wherein said at least one solvent is selected from thegroup consisting of an aliphatic solvent, an aromatic solvent, a polarsolvent, a hydrogen donating solvent, an ionic liquid solvent and anycombination thereof.
 13. The method of any of claims 1-12, wherein saidsolvent extraction is performed with at least two liquid solvents. 14.The method of claim 13, wherein a first solvent is a polar solvent and asecond solvent is a hydrogen donating solvent or vice versa.
 15. Themethod of any of claims 1-14, wherein said solvent extraction is asingle stage solvent extraction, multiple single stage solventextractions, a single multistage solvent extraction, multiple multistagesolvent extractions or a combination of single stage and multistagesolvent extractions.
 16. The method of any of claims 11-15, wherein saidsolvent extraction is performed at a temperature less than the criticaltemperature of said at least one solvent.
 17. The method of any ofclaims 1-16, wherein said solvent extraction is performed at less thanor equal to 350° C.
 18. The method of any of claims 1-17, wherein saidsolvent extraction generates a mass percentage of gas less than or equalto 5%, excluding water vapor.
 19. The method of any of claims 11-18,wherein one of said at least one solvents comprises tetralin(1,2,3,4-Tetrahydronaphthalene), 1-methyl-napthalene, toluene,dimethylformamide (DMF) or any combination thereof.
 20. The method ofany of claims 1-19, wherein said solvent extraction is performedupstream of said pyrolysis.
 21. The method of any of claims 1-20,wherein said pyrolysis is performed upstream of said solvent extraction.22. The method of any of claims 1-21, wherein a portion of products forsaid pyrolysis step are recycled to said solvent extraction.
 23. Themethod of claim 22, wherein said processing step comprises multiplesolvent extractions and products from a later solvent extraction arerecycled to an earlier solvent extraction or said pyrolysis or used asan intermediate for upstream further processing.
 24. The method of anyof claims 1-23, wherein said feedstock at least partially derived fromcoal is greater than or equal to 90% unrefined coal by weight.
 25. Themethod of claim 24, wherein said unrefined coal is physically,chemically or thermally preprocessed prior to said step of processing.26. The method of any of claims 1-25, wherein a portion of saidfeedstock is one or more product streams from said pyrolysis, saidsolvent extraction, recycle streams or a combination thereof.
 27. Themethod of any of claims 1-26, wherein said feedstock at least partiallyderived from coal comprises subbituminous coal.
 28. The method of any ofclaims 1-27, wherein said feedstock is at least partially derived fromcoal is derived from run of mine coal.
 29. The method of any of claims1-28, wherein said high value coal products comprise less than or equalto 10% fuel products.
 30. The method of any of claims 1-29, wherein saidhigh value coal products comprise polymers or polymer precursors. 31.The method of any of claims 1-30, where said high value coal productscomprise polyurethane.
 32. The method of any of claims 1-31, whereinsaid high value coal products comprise composite polyurethane foam. 33.The method of any of claims 1-32, wherein said high value coal productscomprise polyamides.
 34. The method of any of claims 1-33, wherein saidhigh value coal products comprise polyesters.
 35. The method of any ofclaims 1-34, wherein said high value coal products comprise adhesives.36. The method of any of claims 1-35, wherein said high value coalproducts comprise aromatics.
 37. The method of claim 36, wherein saidhigh value coal products comprise benzene, toluene, xylene, phenols,cresols, xylenols, naphthenols, C9 single aromatic rings, C10 singlearomatic ring isomers or any combination thereof.
 38. The method of anyof claims 1-37, wherein said high value coal products compriseparaffins, olefins or a combination thereof.
 39. The method of any ofclaims 1-38, wherein said high value coal products comprise asphaltenes.40. The method of any of claims 1-39, wherein said high value coalproducts comprise coal tar, distillates, pitch, carbon fibers or anycombination thereof.
 41. The method of any of claims 1-40, wherein saidhigh value coal products comprise soil amendments
 42. The method of anyof claims 1-41, wherein said high value coal products comprise buildingmaterials.
 43. The method of any of claims 1-42, wherein a significantportion of said high value coal products are solids.
 44. The method ofclaim 43, wherein said solids can be converted to constructionmaterials, composite materials, liquid additives or any combinationthereof when combined a resin, liquid or other bi-product generated bythe methods described in claims 1-43.
 45. The method of claim 44,wherein said extracts can include metals and rare earth elements.
 46. Amethod for converting coal into a plurality of high value coal productscomprising: providing a primary feedstock at least partially derivedfrom coal; processing said primary feedstock, wherein said processingsequence is: a pyrolysis step, wherein said pyrolysis step is performedin less than or equal to 10 seconds performed in a hydrogen richatmosphere; and a solvent extraction step, wherein said solventextraction step is performed with at least one liquid solvent, whereinsaid liquid solvent is selected from the group consisting of: a polarsolvent, a hydrogen donating solvent and any combination thereof;wherein said pyrolysis step is the first processes step performed onsaid primary feedstock and said solvent extraction step is the secondprocess step carried out on a solid char produced from said pyrolysisstep; and wherein said pyrolysis step and said solvent extraction stepare integrated and carried out under conditions for generating aplurality of high value coal products.
 47. The method of claim 46,wherein said pyrolysis step is a flash pyrolysis process.
 48. The methodof claim 46 or 47, wherein said solvent step process is a single stagesolvent extraction, multiple single stage solvent extractions, a singlemultistage solvent extraction, multiple multistage solvent extractionsor a combination of single stage and multistage solvent extractions. 49.The method of any of claims 46-48 wherein said solvent extraction stepuses two or more solvents.
 50. The method of any of claims 46-49,wherein processing said feedstock further comprises one or moreseparation steps occurring after said pyrolysis step, after said solventextraction step or in between multiple solvent extractions.